Preparation of a soluble metal quinolinolate



as amest-525s ratclucu nugat saucdugsa ees Price Victor N. Kalberg, Chicago, Ill., assignor to Scientific Oil Compounding Company, Inc., a corporation of Illinois No Drawing; Application July 10, 1950,

V Serial No. 173,013

7 18 Claims.

This invention relates to s c-called permanent fungicidal and/or fungistatic compounds or com positionsand to methods of making the same.

The compounds of the present invention are formed by reacting a phenol with a water-insole uble metal quinolinolate. The proportions of the reactants may be varied widely, as desired. They may be. stoichiometrical proportions, but it is preferred that asubs-tantial molar excess of the phenol be used. A molar excess of the waterinsoluble metal quinolinolate may be used, but this is not desirable. The reaction temperature may also be varied widely, as desired, from room temperature or even below up to the lowest decomposition temperature of the reactants. It is preferred tofcarry out the reaction at an elevated temperature at about the melting point of the phenol where the phenol is normally a solid at 70 F., and at or a little below the boiling point of the phenol where the phenol is normally a liquid at 70 F;

The compounds of the present invention are capable of being dissolved or dispersed readily in one or more of the common organic solvents such as benzol, toluol, methanol and acetone, and in oils and oily materials such as vegetable oils, fish oils, and mineral oils, molten rosin, and the saturated and unsaturated higher aliphatic acids containing from eight to eighteen carbon atoms,

or in a mixture of such materials. The resultin [solutions or dispersions have usefulness as fungicidal and/or fungistatic sprays, impregnants and coatings in the treatment of canvas, webbing, threads, yarns, rope, cord, wood, paper, leather,

' resins, and the like. The compounds of the present invention may be incorporated in varnishes, sealers, lacquers, paints, and the like, and the resulting products are thereby made fungus-resistant. Phenol-aldehyde resins, urea-aldehyde resins, melamine-aldehyde resins, polymerizable polyester resins, alkyds including unsaturated "alkyd resins, vinyl resins, polyethylene resins as vention.

The water-insoluble metal quinolinolate react- ,an-t may be an alkaline earth metal salt,- a heavy metal salt, or an aluminum, tin or beryllium salt of an hydroxyquinoline having the phenolic hyadroxy group located in anyposition in the ben- 2 z-ene nucleus or the nitrogen ring of the quincline radical, or in more than, one suchpositlon. Examples of these salts are thecalcium, barium, magnesium, beryllium, lead, mercury, manganese, cobalt, nickel, iron, copper, cadmium, silver, thallium, tin, zinc and aluminum salts of 2-hydroxyquinoline, 4 methyl-2-hydroxyquiholine, -hydroxyquinoline, 2-methyl-4-hydroxyquinoline, 5-hydroxyquinoline, fi-hydroxyquinoline, 7- hydroxyquinoline and B-hydroxyquinoline; The preferred compounds of the present invention are the products formed by reacting a phenol with a heavy metal salt, particularly a copper salt,'of S-hydroxyquinoline. Examples of these salts are copper--8-quinolinolate, copper 5,7-dichloro-8- quinolinolate and copper 5,7-dibromo-8-quinolinolate.

Of the Water-insoluble'metal quinolinolate reactant-s which may be used copper-S-quinolinolate is preferred because it is commercially available and because it reacts readily with a phenol to produce compounds in accordance with the present invention having superior fungicidal and/or fungistatic properties. These. new comare corresponding dispersions of copper-B-quinolinolate.

Any phenol may be used as a reactant in accordance with the present invention but Ipre'fer to use a phenol of the general formula wherein X represents the following radicals; H, OH, CHO, N02, Cl., Br., alkyl, aryl, alkaryl, aralkyl, CONHz, COOR and OR and n represents an integer, 1 to 5; and wherein the R of the radical COOR represents H, alkyl and aryl, and the R of the radical OR represents alkyl and aryl. The X substituents may be alike or dissimilar, as desired. Examples of phenol compounds falling within the ambit of this-general formula are phenol, ortho amyl phenol, para cresol, ortho cresol, meta cresol, para chloro meta btiiiibi'l KUUM D 3 5M333 Riiia 2,608,556 3 4 e501, tertiary bu yl meta cresol, para, it phe Emampze 2 I101, salicylaldehyde, salicylamide, ortho cyclohexyl phenol, resorcinol, pyrogallol, 2,4-dichlorophenol, pentachlorophenol, picric acid, thymol (5-methyl-,-2.,- is opropyl phenol),- ZBAfi-tetrachlorophenolf tetiach'lorohydroquinone, v 6-tertiarybutyl-3-methypheno1, xylenol, chloroxylenol, 4-

phenyl phenol, 2,4,6-tribromophenol, para tolyl-i;

phenol, xylyl phenol, phenyl salicylate, para hydroxy propiophenone, methyl salicylate;2,2 di z hydroxy 5,5 dichlorodiphenylmethane (G 1) and. any mixture thereof. The s-Gr-tcompound is also known as bis(5ch1oro=2-hy droxyphen-1 yl) methane.

The following are illustrative, examples of method of preparing the reaction products -oii the present invention. The reaction, in each in'-' stance, was carried out in a glass (Pyrex) greace tion vessel with constant stirring of the reactants;- however,- it; may be carriedout in atreacs tipn' vessel mada-of stainlesssteel .or otheanon-n comio iblesmaterial,v In. these examples theterm- .papt; refers-topartsby weight.-

Eiramplcji,

. 100 parts of salicylamide were heated to 300' F. and- 11 parts of "copper-8 quinolinolate were then added: with stirring." The mixture'was then further heated. to 320 F3; resulting in complete solution pa'rts of the resulting reaction product;

werefthen:dissolvedvina solvent mixture consist ing ..of. 605 parts 1; toluol, 20 parts methanol f and lol artszmorpholine and the-solution. was used toimpregnate duck: samples which were' the testedi asfollows.

Samples of 10 oz. specification army duck -werecut into' 6"X-30" pieces 'and the-pieces were washed in soapsuds; rinsed thoroughly and dried." Onepiece was submerged at room temperature-in-the above 10%so1-ution-of'-th'e reaction. product and passed througha set "of rubber squeeze rollers to remove the excess. of impreg nating solution. Approximately a 50% '.wetpickup was obtained a'n'd'the impregnated fabric was then air-dried atroom temperature for 48' hours" to insure substantially. complete solvent, release.

I 'Ijh'eimpregnated and dried piece of duck was. buried in a well com osted soil consisting of 50% black loamand 50% -pre-rotted.manure,- hori-- zontally one-inch beneath the surface of the soil for 14 days. which-was usedcas acontrol was similarly buried.-

During this period. the-soil? temperature was: maintained at approximately-80 with -ap were removed from the soil; washed thoroughly inwarm water toremove all soil particles and air dried-at room temperature. Tensile strength on' the treated piece was thentaken on the :same' Scott tester. It had atensile-strength of 223 lbs. The-contror'p-iece was removed from" the soil in small deteriorated pieces which had lost their" fabric strength and hence were not tested. Each of these small pieces was badly stained. Incorrtra'st the treated-piece was substantially free from stain:-

A similar piece of untreated duck solu-tionof .this example showed slight to no evidence'. of microorganism attack and showed no loss of fabric strength. The control specimen was removed" from the soil ,in small pieces, badly stained and with complete loss of fabric strength.

Es'rample. .3.

parts by weight of para chloro meta=cresoli were meltedand: heated to-125 -to 150" 15 parts of copper 8 quinolinolate were added with -sti'r'- ring. A 'clear..solution resulted; The solution solidified oncooling to room temperature." The solid 'dissolved: readily in .toluoL- benzol, metha'nol andacetone, and in "mixtures of th'esesolvents'fi 10 parts by weight of the' reaction "product were dissolved in parts: of 'a'cetone and a piece ofduck simil'ar to that irr Eirample- 1 wasdmpregmated with this solution %and further treatedand buried inxsoil alongiwith 1a: control p'iecei alll a's' de'scribediin'Exam'pl 1.

The duck? specimen treated wi'th th treating; solution of'thisilexample showed sli'ght'to no evi denoe iof microorganismi:attack and showedloss: of fabr ic; strengths I The :contr'ol specimenwas: removed-drum thesoiiinsmall pieced-badly stained and with complete loss of fabric strength:

' Emamplecell 90 'parts"*by weight ioff'para' nitro. phenol were melted;by.heating to 260 F". 10 "parts'of "copper; 8-jquinolino1ate were added LWith'stirringto the; molten mass; sufiici'ent 'heati'being. "supplied 'to" maintain] in" the melt. temperature of 72501 to 275963; The meltj solidified on curing. The resultingsolid dissolved to an extentislightly.less, than2%in"to1uo1,benzolfmethanoliand acetone.

A: 1.5 solution. of the reaction. productf'of this example" iir-toluol 'waspreparedi and aipiece; of duck similar to that 'of:' Examp1e' '.1I was impregnated with this solution an'd 'furthertreated and buried in soihalong with a" control" piece, alias describedinExamplell V Theiduck specimen treated .with thez treating solution-50f this example showed "Islight 'to" no evidence of microorganism attack: and showed no 'lossfof "fabric strength? The. control specimen was removed from the soil in small pieces badly stained andwith complete loss of fabriostrengthy V Estample t A 80j'p'artsof 2,?le'dichlorophenolwere meltedhndl heated to" 'F. 20'lparts of copper-8 quinoe lino'late were added withi stirring, resulting in. completesolutibn which solidifi'd"on cooliii oi room temperature. The solid was soluble. n toluol',fbenzoLmethan'ol and acetone.

Apiecepf 'duck similar to that in Eizample'l was; impregnated "with a 10%": solution of the reactiongproduct .of this example in jbenz'ol' and the impregnated piece of duck'was rurth'ertreat:

ed andburied-in soil along with a control piece, all as describedin Example 1. v V

The duck specimen treated with the treating solution of this example showed slight to no evidence of microorganism attack and showed no loss I 01' fabric strength. The control specimen was removed from the soil in small pieces, badly stained and with complete loss of fabric strength.

Example 6 '90 parts of phenol were melted and heated to 150 F. parts of copper-8-quinolinolate wereadded with stirring, resulting in complete solution which solidified on cooling to room temperature. The solid was soluble in toluol, benzol, methanol and acetone.

A-piece of ducksimilar to that in Example 1 wasimpregnatedwith a 10% solution of the reaction product of 'this example in toluol and the impregnated piece of duck was further treated and buried in soil along with a control piece, all as described in Example 1.

The duck specimen treated with the treating solution of this example showed slight to no evidence of microorganism attack and showed no loss of fabric strength. The control specimen' was removed from the soil in small pieces, badly stained and with complete loss of fabric strength. 1 j Example 7 85 parts of .pentachlorophienol were melted and heated to 375 F. parts of copper-8- quinolinolate were added with stirring, resulting in complete solution which solidifiedon cooling toroom temperature. The solid was soluble in toluol,,benzol, methanol and acetone.

A pieceof duck similar to that in Example 1 was impregnated with a. 10% solution of the reaction product of this example in benzol and theinipregnated piece of duck was further treated and buried in soil along with a control piece, all as, described in Example 1.

The duck specimen treated with the treating solution of this example showed slight to no evidence'of microorganism attack and showed no loss of fabric strength. The control specimen was removed from the soil in small pieces, badly stained and with complete loss of fabric strength. Example 8 '85 parts of resorcinol were melted and" heated 15' parts of copper-Zi-quinolinolate were added with stirring, resulting in complete solution which solidified on cooling to room temperature. The solid was soluble in toluol, benzol, methanol and acetone.

. Aypiece of duck similar to that in Example 1 was-impregnated with a 10% solution of the reaction product of Tthis example in methanol and the impregnated piece of duck was further treated'and buried in soil along'with a control piece, all as described in Example 1.

. The duck specimen treated with the treating solution of this example showed slight to no evidence of microorganism attack and showed no loss of fabric strength. The control specimen was removedfrom the soil in small pieces, badly stained and with complete loss of fabric strength.

Example 9- linolatewereadded with stirring. resulting in complete solution whichlsolidifled on cooling to room temperature. The solid was soluble in toluol, benzol methanol and acetone. 7' A- piece of duck similar to that in Example 1 was impregnated with a 10% solution of the reaction product of this example inacetone and the impregnated piece of duck was further treated and buried in soil along with a control piece, all as described in Example 1.

The duck specimen treated with the treating solution of this example showed slight to no evidence of microorganism attack and showed no loss of fabric strength. The control specimen was removed from the soil in small pieces, badly stained and with complete loss'of fabric strength.

Example 10 I parts of thymol (5-methyl-2-isopropyl phenol) were melted and heated to 150 F.f 15 parts of coppenS-quinolinolate were added with stirring, resulting in complete solution which solidified on cooling to room temperature. The solid was soluble in toluol, benzol, methanol and acetone. V

A piece of duck similar to that in Example 1 was impregnated with a 10%. solution of the reaction product of this example in toluol and the impregnated piece of duck was further treated and buried in soil along with a control piece, all as described in Example 1. I

The duck specimen treated with the treating solution of this example showed slight to no evidence of microorganism attack and showed no loss of fabric strength. The control specimen was removed from the soil in small pieces, badly stained and with complete loss of fabric strength.

Example 11 85-parts of 2-4-6 tribromophenol were melted and heated to 225 F. 15 parts of copper-8- quinolinolate were added with stirring, resulting in complete solution which solidified on cooling to room temperature. The solid was soluble in toluol, benzol, methanol and acetone. 1

A piece of duck similar to that in Example 1 was impregnated with a 10% solution of the reaction product of this example in benzol and the impregnated piece of duck was further treated and buried in soil along with a control piece, all as described in Example 1.

The duck specimen treated with the treating solution of this example showed slight to no evi: dence of microorganism attack and showed no loss of fabric strength. The control specimen was removed from the soil in small pieces, badly stained and with complete loss of fabric strength;

' Example 12 parts'of pyrogallol were melted and heated to 285 F. 5 parts of copper-8-quinolinolate were added with stirring, resulting in complete solution which solidified on cooling to room temperature. The solid was soluble in toluol, benzol, methanol and acetone.

A piece of duck similar to that in Example 1 was impregnated with a 10% solution of the reaction product of this example'in methanol and the impregnated piece of duck was further treated and buried in soil along with a control piece, all as described in Example 1.

The duck specimen treated with the treating solution of this' example showed slight to no evidence of microorganism attack and showed no loss ofifabric strength. The control specimen was removed fromthe soil in small pieces, badly stained and with complete lossof fabric strength.

sample r ,9 p arts' of para hydr ogy wprr'mioplflenzline were 'lted' and heated to 285?:FL'1-0 partsotccpperm thane were added with fist-arms, 185111 complete solution which solidifiedon cool roointemperature; I The; solid was: soluble m ,iii 1 0' in toluol, benzohrinethanol and.acetone.

, A piecejof, duck isimilarrto that rin Exa nple 1 m re n Wi h-a '%-1- ien; r the :rs- ,BlfitlOll pro uct otthis. exainple in toluo-l-andr the Timpregnatedpieceof duck vlfas further treated lfandg buified i son; along vg ith a control piece,;all a describedinJilxampled; I r

The duck specimen treated with the treating solution of this example showed slight to no evidence .of lnicroorganism attack .and showed no l s -of ifabr'ic strengt Thencontrol,specimen was remov d; from the il in sman; pieces, badly fst' in'dan "with comp ete 'lo'ssbf; rabrie' st engt soiution of this example showed slight to no evidence of microorganism attack and showed no loss of fabric strength, ,The control specimen wasr mbvecr gm the-soil in, "man pieceszbadly fs'tairied andwith' complete loss of fabric strength.

" Err mple l 1 "asserts o'fnori yl phenolwereheated-to 1'75-F. and 15 parts-ofc' pens-q olinol-ate were then T g; resu tin gdn completesoluuncu eifiaiihed 1iquidon'cooling td room Th '1id1iid reaction-product was "cluol; benz'ol, methanol and-acetone. ii A piece- 6f d'ucit s'iinilarfto that i Example 1 was impregnated with a -'%==s oluti01fi of the-reac'tion produc t of this example in tolubland the impregnated? 'p'i'ece of duck was further treated and: buried insoilalong with a cor'itrol piece; an asidescribd:iii-Example 1.- i

3Tlieduek'. specimen treated with. the treating dence of micro-organism attack and showed no loss of fabric strength. The control specimen wasremoved :from the so'il jin smallj-piecesy liafdly stained-andwith=complete loss-"of fabric strength".

Examplelm I .95 parts oflmethyl salicylate were heated :to 260 and 5 parts of copper-S quinolinolate were then added with stirring; resulting-win com- .plete solution. which; remained liquid on cooling to; room-temperature; The liquid reactionrprod not-was selublei-n toluol-,-benzo1, methanol and acetone A piece of duck similar to that-inExample 1 was impregnated with 'a-10-%- solution of the reaction product ofthis example inzt'oluol .andathe impregnated :piece of duck "was: ifurther treated and? buried in soilialon'g' witlr avc'onti'olvpiece, all as describ'ediin Example'ilr-x r j ;.-'lhe:qduck;= specimens treated with: the? treat? wood: and leather specimens.-

solutions described above imay be us ifig soiutiesatr dais es-"tin" 'sht'te engines in evidence of micro-or g scribed, were individuali y apfiiid to wood samples 1" x 3" andleatheig squares 2" x 2" by soaking under vacuum for'2'0minutes and drying for s hourss. .The treated sspcimens rand unti'eated 'rcontrol-"specimens D'frsimil'ar dimensions wei'e'c'placed onaa sterile' inutrieiituagaiimedlum with 1:3; ti-pH T'Of- 5'55; 'whicH-1W'as Used -1-f61 the islftbi- .dish'; The specimens in": :each eof =".Lthesef:illshes were sprayed withrarspore'suspensiomofrtlieefol e lowing organisms and: incub'ated'iat "3.09:; oarmmm days: Ch'aet'omium iglobosum, i'Penicilliiimcfcitr'rnum, Aspergillus nigenrAspergillus ferreus Trich'oderma: virid'e, andznspergilluszflaiiusi;

, At the conclusion of: this test peiiodi found that fungi were Y growing-Soverwthe; entire surface of the leather? and iwoo'dvfcontrol'zspeci mensand that no growth existed zon-ztheztreated The reaction products of the present hive tion can be used to treats-textiles; paper, leather and the like by irnpregnafi g or coating these materi'a ls with a solution or disp'ersion er; 'tion product in "aQsfuitable vehicle,

these materials. 'lfh esejsoluti'o y a ve t lecandljfisf'h oils, plasticizers; .drie'r's, tgariti-oindants the like, in accordance with known, techniquesf' to impart to the solutions desiredpfopert 'r example, characteristics such as spread of these solutions mayj b" modified M 7 tion thereto of a may dg udh" as au'ric oleic acid,,linseed toil' fatty' ac s; henipsee .ioil i y cids d l atty a s n ifr to 2 0 carbon atoins'intheehain and of, fatty acid glyceride, eitherraw or treated, such. as raw or'bodied linseed oil,' C' hina wood oil, caste on, dehydrated castor oil, an'dlthe likeQQo'm atilile natural and synthetic'resins such as" I'd n nol-aldehyde resins, urea-aldehyde resins, v nyl resins and the like, 'df'biifriatible cellulose deriyatives such as, nitrocellulose;cellulose? acetate, ethyl-celluloseandrthe like-may be incorporated inthesolutionsi iin varyingiproportlons' ito meet any-*desired-needs.-- Plasticizers such-gas; glyeo "rglycerine pentaierythritol, sorbitol, mannito -:and: 10131161? com; patible plasticizers smayberaddetl 'to solutions. Suitable anti-oxidantscwhichtfma ibe added to the solution: are *ph'eny'lsalicylatm eretiarybu-t lcateciiol "and gum-C01; and suitable driers are zincxnaphtlienatejlead naphtheifate, cobalt naphtheriaterafid zinc'octoatet I If it-is desire'd wimp-art:water-proofs ties to the solutions-10f. the reaction produc or the" present invention, -1 Various waxes :su'ci-iparafiin'wax, bees waif, cainaubawas fieimaeai wax,synthetic"waxesfandthe' l a co'rpora'ted mime "soiutiofis' in vary tions to meet the desired needs.

By a proper choice of the solvents for the reaction products of the present-tinvntion an of suitable --modifying agents, 17 the" fs'iiltirig lid d compositions mayibe controlledsas' to consiste drying-timar. flow; penetration; atid th lilf' The reaction products of the present invention need not be used in solution or dispersion form but may be incorporated directly in resins, greases, waxes and similar compositions by compounding these reaction products with other constituents of the compositions in accordance with known techniques. Better distribution of the reaction products in these compositions are obtained if the reaction products are dissolved or dispersed in a suitable vehicle.

Compositions containing reaction products of the present invention not only inhibit the growth of fungus organisms but may also kill the activity of all existing fungus growth on contact. Textiles, leather, wood, resins, etc., which have been treated with the reaction products of the present invention are not attacked to any appreciable extent by soil animal life and these treated ma terials resist the action of bacteria and insects. The reaction products of the present invention lend themselves for use as insecticides, in either dry or liquid form, and for preventing and combating diseases of plant life, both those diseases which attack the parts of plants above ground and diseases such as rot which attack underground parts of the plants.

While the present invention has been described in connection with certain specific examples of methods of making the reaction products, it is obvious that my invention is not to be construed as limited to the specific materials disclosed in these examples or to the details of the methods set forth therein, since changes in materials, proportions and method details may be made with out departing from the scope of my invention as defined in the appended claims.

I claim:

1. The method of making a material having fungicidal properties comprising maintaining a mixture of a phenol and water-insoluble meta quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and quinolinolate until the quinolinolate dissolves in the phenol.

2. The product formed by the method of claim 1.

3. The method of making a material having fungicidal properties comprising maintaining a phenol and quinolinolate until the quinolinolate dissolves in the phenol.

6. The product formed by the method. of claim 5.

'7. The method of making a material having fungicidal properties comprising maintaining a mixture of a phenol and copper 8-quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and qinolinolate until the quinolinolate dissolves in the phenol.

8. The product formed by the method of claim '7.

9. The method of making a material having fungicidal properties comprising maintaining a mixture of phenol and copper 8-quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and quinolinolate until the quinolinolate dissolves in the phenol.

10. The product formed by the method of claim 9.

11. The method of making a material having fungicidal properties comprising maintaining a mixture of nonyl phenol and copper 8-quinolinolate at a temperature below the lowest decomposition temperature of the said .phenol and quinolinolate until the quinolinolate dissolves in the phenol.

12. The product formed by the method of claim 11.

13. The method of making a material having fungicidal properties comprising maintaining a mixture of ortho amyl phenol and copper S-quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and quinolinolate until the quinolinolate dissolves in the phenol.

14. The product formed by the method of claim 13.

15. The method of making a material having fungicidal properties comprising maintaining a mixture of salicylamide and copper 8-quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and quinolinolate until the quinolinolate dissolves in the phenol.

16. The product formed by the method of claim 15.

17. The method of making a material having fungicidal properties comprising maintaining a mixture of 2,4-dichlorophenol and copper 8-quinolinolate at a temperature below the lowest decomposition temperature of the said phenol and quinolinolate until the quinolinolate dissolves in the phenol.

18. The product formed by the method of claim 1'7.

VICTOR N. KALBERG.

No references cited. 

1. THE METHOD OF MAKING A MATERIAL HAVING FUNGICIDAL PROPERTIES COMPRISING MAINTAINING A MIXTURE OF A PHENOL AND WATER-INSOLUBLE METAL QUINOLINOLATE AT A TEMPERATURE BELOW THE LOWEST DECOMPOSITION TEMPERATURE OF THE SAID PHENOL AND QUINOLINOLATE UNTIL THE QUINOLINOLATE DISSOLVES IN THE PHENOL. 